Manufacture of sodium hydrosulphides



, purities, particularly iron.

phide may be formed by gassing; sodium sul- Patented May 22, 19.45

, UNITED STATES PATENT orrlcs MANUFACTURE OF SODIUM HYDROSULPHIDES Charles Louis Koenig, Syracuse, N. Y., assignor to The Solvay Process Company, NewYork, N. Y., a corporation of New York Nollrawinl. Application March is, 1944,

. Serial No. 527,143

11 Claims. (c1. 23-134) This invention relates to manufacture of sodium hydrosulphide (NaHS) or sodium sulphide (NasS) or mixtures of both.

With the exception of a very small amount, all

commercial grades ofsodium sulphide are made i from salt cake (NMSOO or nitrecake (NaHSOr) by reduction with coal or coke at elevated temperatures. The reaction is usually carried out in reverberatory or rotary furnaces, and the furnaced material isput thru a relatively elaborate and cumbersome NarS recovery and purification procedure. Such process is inherently complicated and costly, and moreover results in an end product containirig a substantial quantity of imhydrosulphide liquor with hydrogen sulphide. Also, sodium sulphide may be made by treating an NaHS liquor with sodium hydroxide.

It is. known that sodium carbonate (Na'zCOa) reacts with Has to form NaHS. Attempts have been made to produce NaHS by gassing a. liquor containing sodium carbonate withhydrogen sulphide. While these proposals bring about formation of some NaHS which remains in solution, it was observed that the proportion of the sodium content of the liquor subjected to gassing which I precipitated as sodium acid carbonate (mostly Na:COa.NaHCO:.2H:O and NaHCOs). was so great and the loss of sodium as precipitate was so high as to render processes of such nature uneconomical. My investigations indicate the foregoing difflculties are attributable to lack of knowledge 0! conditions under which the H28 gassing operation should be carried out. Asiar' as I know, there i no commercial production of sodium hydrosulphide or sodium sulphide by reaction of sodium carbonate and hydrogen sulphide.

A major object of this invention lies in proate necessarily formed during HJS gassing may be eflected to such an extent that the amount of sodium acid carbonate carried in solution in the liquors in the system is held at an economical low level, and (2) good conversion of NazCO: to NaHS maybe obtained. Further purpose or the invention is to aflord accomplishment of the foregoing objects and at the same time utilize, as a sourceof H23, commercial hydrogen sulphide gases, e. g. from petroleum refining operations. containing substantial amounts of carbon dioxide the presence of which normally tends to increase formation of sodium acid carbonate.

While it is evident to me that sodium acid can bonates, which tend to separate out in solid phase from liquors such as handled in the invention process, include sodium sesquicarbonate, NazCO3.NaHCOz.2I-h0, and decimite,

NazCOaJiNaHCQ as well as a major amount of sodium bicarbonate itself, unless otherwise specified, mention of sodium bicarbonate herein is intended for convision of a process for makingsodium hydrosulphide or sodium sulphide. ofpurity acceptable to the trade, using as raw material commercial.

grades of soda ash (Na-200s) and impure hydro,- gen sulphide gases which are readily available commercially. Practice of the invention involves assing an aqueous solution containing sodium carbonate with an HzS gas to efiect reaction of 'NazCOa and HaS to form NaI-IS. From an operating standpoint, a chief object of the invention is provis ion of processes the practice of which venience to include all sodium acid carbonates present. i

The process of the invention comprises two major stages: first, formation of aqueous sodium carbonate starting liquors of certain compositions, utilizing commercial soda ash as the raw. material; and second, a reaction stage in which Product solutions to such an extent as to render the process economical.

I find that the aqueous carbonate of sodium 1 starting liquor should have in solution a total sodium salt content of not morethan 21% by makes it possible to carryout the'sodium carbonate liquor-Has gassing operation in such a way as to prevent formation of carbonate containing solid phase which notonly plugs up the more usual types of gas contacting apparatus but also causes heavy loss of sodium as a sodium acid carbonate of one kind or another. Other importantobiects are to provide procedures by which (1) decomposition of sodium acid carbonweight, expressed as NazCOa. In this specification and appended claims, the expression total sodium salt'content is used to define the sum of'any .or all of the sodium salts of the group consisting of the carbonate; bicarbonate, bisulphide, and sulphide of sodium. The preferred starting solution is an atiueous'NazCO: solution containing substantially no sodium salt other than NazCOrand having an NaaCO: concentration of not less than 10% and not more than 21% by weight. Such a solution may be made up by adding the proper amount of commercial soda ash to water. The starting solution may contain some NaHS, some sodium acid carbonate, possibly some NaaS, or some of any two or all three,

' but preferably the sodium salt present should be predominantly NaaCOa as such, and in any case 5 preferably as concentrated 'as possible, and new 1 ally are water solutions of sodium carbonate having NaaCOa concentrations of 18-20% byweight.

A second control factor of importance is the temperature at which gassing oi' the sodium carcourse of H23 gassing, NaaCOa reacts with we Y to produce NaI-IS and NaHCOa. At certain temperature conditions, much of the NaHCOa formed may bebroken down by heat to-COa, water and NazCOa, and such NasCOs is made available for 2 reaction with further ms to make more NaHS. I have found, in conjunction with utilization of the above described starting liquors, that in order to enhance reaction of ms and sodium carbonate, to prevent formation of carbonate containing solid phase, .to hasten decomposition of sodium acid carbonate and effect stripping out and discharge-from the contacting zone of C02.

initially combined with NaaCO: and thus minimize the quantity of sodium aciid carbonate 3o held in solution in the liquor in the contacting zone, the sodium carbonate-H28 gassing operation should be carried out while maintaining, in the contacting zone, temperature not less than 7 100 C. and not more than 125 C. Preferred of greatly increased equipment corrosion.

A third control condition of importance during HqS gassing is regulating the contacting operation so as to prevent, during the course thereof, increase of total sodium salt content" of the solution to more than 21% by weight, expressed as NaaCCh, since higher total sodium salt content should be avoided to prevent formation of carbonate containing solid phase. Such regulation of the contacting operation is dependent upon the total sodium salt content of the particular starting solution used, and also upon the temperature at which any specific gassing operation is being carried out. As previously indicated, starting solutions usually employed are those having a total sodium salt content". (pref- 60 erably all NazCOa) of the order of 18-20%. It will be seen that, when utilizingstartlng solutions of this relativelyhigh total sodium salt content, there is not much latitude for solution concentration during ms gassing before a total '65 sodium salt content-equal.to 21% by weight, expressed as NaaCOs, would be reached. Hence in this case, very little if any solution concen-' tration should be permitted during H28 gassing,

and to provide for this situation, regardless of v plurality of contacting towers may be employed the particular reactionternperature being'used.

' it is preferred to carry out gassing under pres- I sure conditions such as toprevent any substantial boiling of the solution being. gassed. Bpeciflc pressureto be used dependent upon the 76.

particulartemperature prevailing in the reaction zone. Solutions of the type employed for H28 gassing in accordance with the present invention have boiling point of the order of C. Thus, if reaction zone temperature is say l00- 103 C.,-it is possible to proceed at atmospheric pressure without losing. enough water vapor to cause detrimental total sodium salt concentration. However, preferred reaction temperatures are 105 C. or above, and accordingly it is preferred to subject the solution being gassed'to superatmospheric pressure suflicient to prevent any substantial boiling to thus avoid loss-of water vapor and corresponding total sodium salt bonate solution with ms is carried out. In the content" concentration. Pressures up to 30 lbs.

. gauge may be used, pressures in the preferred temperature range of l05-ll5 C. being about 5-20 lbs. gauge.

when using starting solutions having total sodium salt conten substantially-less than 21% by weight, expressed as Naacm, it should be 7 understood that appreciable total sodium salt content" concentration during .gassing is permissible without increasing the total sodium salt content" of the solution to more than 21% by weight. expressed as Nae-CO3. Thus when using relativeiy weak, say of the order of 15% total sodium salt content," starting solutions, boiling of the solution undergoing gassing may be-per mitted until the "total sodium salt content approaches 21% by weight, expressed as NazCOr.

The gassing operation may be carried out in any satisfactory liquors-gas contacting apparatus. The H28 gas may be bubbled thru a relatively static'body of starting liquor. However, it is preferred to eifect reaction in a countercurrent tower of suitable design. The tower may be packed, e. g. with suitably sized'coke or say 1 inch Raschig rings, or packing may be 40 omitted and the tower preferably provided with bailie'sv arranged to afford good contact of gas and liquor and controllable retarded downfiow of liquor. Whatever type of contacting appsr'atus is employed, it will be understood that construction is such as to include the accessory equipment needed to provide for introduction of the starting li'quoninto-the top of the reaction zone against whatever-pressure there may be therein, control of rate of feed of incoming liquor, discharge ofireacted liquor, maintenance throughout the contacting zone of the indicated temperatures-land whatever pressures may be I contact in such a way. that satisfactory reaction of sodium carbonatezand H28 may be had during a single pass of liquor thru the tower. In this situation, whether packed or provided with bames, it will'be understood that design of tower,

rate of feed of starting liquor, rate of'introduction of H28 gas and rate of withdrawal of reliquor are such as to-ailord adequate retention of liquor in the contactingzone to ob-' the desired degree of reaction of NaaCO: and

' H28. Gassingmay beei'lected in a relatively small tower provided with means to repeatedlf'recirculate liquor over the-tower. Alternatively, a

m which case, it will be understood. thestarting liquor is fed into the'top time first tower. partly reacted liquor withdrawn from the bottom and fed into the top of a'second tower, and product of the second tower, gas leaving the top of the second tower is fed into the bottom of the first tower and tail gas is discharged from the top.

, Each tower is provided with the necessary means to keep temperatures and pressures existing in the reaction zone within the limits indicated. Temperatures may be maintained by controlled indirect heating. All contacting operations mentioned may be carried out on a continuous basis, 1. e. initial starting liquor and H28 gas may be continuoushr introduced into the system and product liquor withdrawn therefrom.

In practice, the gases which may be employed include pure H28 gas, HIS gas containing diluents inert to the reaction, or an H28 gas containing a' diluent such as CO: which is notinert to the reaction, 1. e. CO: reacts in water solution with NazCOs to form NaHCOz. In the case of H15 gases containing diluents inert to the reaction, H28 concentration may be any feasible value. I find that in order to prevent a build-up of NaH Ca in the system, particularly in a continuous operation, if the H18 gas used contains 00:, such incoming HaS gas should contain,

by volume no more 00: than H28. In all operations, it is preferred to employ gases containing not less than 50% H28 by volume, and if such gases contain CO2, .eoncentration of the latter should be not above 25% by volume, 1. e. CO: content by volume" is preferably not more than half the H28 content by volume. In usual operation, gases utilized comprise about 90% H28 and about 10% CO: by volume. In this specification and appended-claims, gas compositions mentioned are intended to define compositions of the ms gas at the point of first contact of incoming gas with liquor in the system. I have found when utilizing starting liquors of compo sitions described and the gassing temperature and 7 pressure conditions noted, operation proceeds smoothly regardless of relatively large amounts of extraneous CO: brought into the system with the 1128 gas, this feature being one of the advantages of the invention, namely, utilization of commercially available HzS gases which contain substantial amounts of CO2.

In one series of runs using a baflle type tower throughwhich the liquor passed once, a starting liquor consisting of a water solution of soda ash and having an nazcos concentration of about 21% by weight, a hydrogen sulphide gas containmg about 90% H28 and 10% cm by volume. re- 55 eral runs varying from 101 C. to 114 0., there were obtained reacted liquors in which conversions of NaaCO: to NaHS ranged from about 55 I to about 62%, and had compositions as follows: NaHS from about 12 to about 14% by weight;

NaHCOa from about to about 7.5%; Na'iCOa from about 3.5% to about 6.5%; and total sodium salt contents expressed as NazCOa varied from 20 to about 22.5%. Carbonate containing solid phase did not form during gassing.

In other representative runs'using a packed I tower and a single pass of liquor thru the tower, a starting-liquor consisting of a 20% by weight soda ash water solution, and a vgas comprising.

90% H25 and CO: by volume, reaction zone pressure of about lbs. gauge, and-reaction z'one' the reacted liquors analyzed'by weight. NaHS 940%; NaHCO: 942%; NaaCO: 44%; and

- -2l% total sodium salt content" expressed as NarCOs. Carbonate containing solid phase did.

5 not form during gassing.

The reacted liquors contain appreciable quantities of sodium acid carbonate and sodium carbonate, Nat-CO4. Liquors of this type should not be concentrated by the usual evaporation meth- 10 ads in the presence of sodium acid carbonate. without loss of NaHS, since it appears that on heating, sodium acid carbonate causes decomposition of NaI-IS with resultant formation of Na=COa and H28. Hence,'sodium acid carbonate 1 should be removed substantially completely from the reacted liquor in any suitable way. This may be accomplished, for example, by treating emuent liquor of the .reaction zone with caustic soda, resulting in conversion of acid sodium carbonate to NBaCOs and water. Following substantial elimination'of sodium acid carbonate, the liquor may be concentrated as desired to strength of about 50% Nal-IS. During .such concentration, which may be eflected by heating the 2 liquor at, atmospheric pressure to about 150 C most of the NaaCO: precipitates, settles out and may be removed by filtration. The resulting relatively strong NaHB filtrate ordinarily contains in solution about 02-03% NaaCOa in solution, which residual NazCOa maybe removed in any suitable way if substantially pure NaHS end product is desired. If the end product desired is NaaS, the NaHS liquor may be treated with NaOH to convert all or any portion of the NaHS to NaaS. Alternatively. NaHS or Nags maybe produced in solid form by evaporation of the liquors and solidification by known methods. NaaCOa by-product may be returned to the process.

.Two ccpending applications; of Julien and Terziev, Serial No. 522,794, and Arthur W. Saddington, Serial No. 538,101, both assigned to the same common assignee as this application and both directed to'subject matter related to this application, ,were filed on February 17, 1944 and May 30, 1944, respectively.

I claim: v I

i. The method for producing sodium hydrosulphide which comprises forming an aqueous carbonate of sodium solution having a total sodium salt eonten of not more than 21% by weight, expressed as NaaCOs, said total sodium. salt content" being at least-predominantly NaQCOQ, contacting said solution with gas containing H28 and an amount 01' C02 ranging from none to avolume equal tothe volume of the H28 content of said gas, and maintaining, during said contacting operation. temperature not less than 100 C. and pressure conditions such as to prevent anysubstantial boiling of said solution, thereby forming sodium hydrosulphide.

- 2. The method forproducing sodium hydrosulphide which comprises forming an aqueous carbonate of sodium solution containing substantially no sodium salt otherthan carbonate and having a total carbonate of sodium content not more than 21% by weight, expressed as NaaCOa,

' said carbonate ,of sodium content being at least predominantly NazCOa, contacting said solution "with gascontaining H28 and an amount of CO2 ranging from noneto a volume equal to the vol ume of the H25 content of said gas, and maintaining, during said contacting operation, temperature not less than 100 C. and pressure conditions such as to preventany substantial boiling of said solution, thereby forming sodium hydro-' sulphide.

3. vThe method for producing sodium hydrosulphide which comprises forming an aqueous NaaCOs solution containing substantially no' sodium salt other than NazCOa and having an asvassi as to prevent any substantial boiling of said-solution, thereby forming sodium hydrosulphide.

' 8. The method for producing sodium hydrosulgas, and maintaining, during said contacting vent any substantial boiling of said solution,

thereby forming sodium hydrosulphide.

4. The method for producing sodium hydrosulphide which comprises forming an aqueous carbonate of sodium solution having a total sodium salt conten of not more than 21% by weight,

expressed as NaaCOs, said total sodium salt content" being at least predominantly NasCOa, contacting said solution with gas containing H28 and an amount of CO: ranging from noneto 9. volume equal to half the volume of the ms content of said gas, and maintaining, during said contacting operation, temperature not less than 100 C.

and pressure conditions such as to prevent any substantial boiling of said solution, thereby form- ,ing sodium hydrosulphide. 5. The method for producing sodium hydrosulphide which comprises forming an aqueous carbonate of sodium solution having a total sodium salt conten of not more than 21% byweight', expressed as NszCOz, asubstantial portion of said "ftotal sodium salt content being NazCOs, con- 3 tacting said solution with gas containing &8 and an amount of CO: ranging from none toa. volume equal to the volume of the H28 content of said gas while maintaining temperature not less than 100 0., and regulating the contacting operation so as to prevent, during the course thereof, increase of the total'sodium salt content'oi the solution undergoing ms gassing to more than 21% byweight, expressed as NaaCQs, thereby forming sodium hydrosulphide. i

8. The method for producing sodium hydrosulphide which comprises-forming an aqueous carbonate oi sodium solution having a totalsodium 'salt content" of not more than 21% by weight,- expressed as NazCOS, a substantial portionof said total saltcontent being NszCOa, contacting said'solution with gas containing HaSand an amoimt of CO: ranging from none to a volume equll to half the volume of i the ES content of said gas while'maintaining temperature not less than '100' 0., and regulating the contacting operphide which comprisesiorming an aqueous carbonate oi sodium solution having a ftotal sodium salt content" not more than 21% by weight, expressed as NasCOr, said total sodium salt content" being at least predominantly NasCOs, contacting said solution with gas containing H28 and 1 an amount of C0: ranging from none to a volume equal to the volume of the H content "of said operation, temperature not less than 100 C. and not more than 125 C. and pressure not less than 5'and not more than 30 lbs. gauge but at least suiiicient to prevent any substantial boiling of said solution, thereby forming sodium hydrosulphide.

' 9; The method for producing sodium hydrosulphide which comprises forming an aqueous NaaCOa solution containing substantially no si dium salt other than Marco: and having an 1 NBsCO: concentration not less than.'10% and not more than 21%. by weight, contacting said solution with gas containingnot less than 50% Has by volume and an amount or CO: ranging from none to a volume equal to halt the volume of the H23 content of said gas, and maintaining, during said contacting operation, temperature not. less than 105 C. and not more than 115 C. and 1 pressure not less than 5 and not more than 20' lbs. gauge but at least sumcient topreven't any substantial boiling of said solution. thereby forming sodium hydrosulphide.

10. The method for producing sodium hydro- I sulphide which comprises forming an aqueous carbonate oi sodium solution having a-tptal soation was to prevent, during the course thereon. increase of the total sodium salt content'of the solution undergoing H28. gassing; to more 1' than 21% by weight, expressed as NaiCOa, thereby;

forming sodium hydrosulphide.

' "L- The method for producing sodium hydrosul- Y phide which comprises tormingan aqueous 'car-* bonate oi. sodimn,solution having. a total sodium salt: content" or not "more 21% by weight,

"total sodium salt content!" being. NasCOs, contacting'said solution with gas containing H28 and an amount or CO: ranging from none to a volume equal to the volume or the H58 content of-said gas, and maintaining, during said contacting operation', temperature not less 100C. andynot more than 125' conditions such expressed as Na:CO:,-a substantial portion of said dium salt conten 01' not more than 21% by weight, expressed as NazCOa, a substantial portion of said total sodium salt content being NazCOa, introducing said solution into a reaction zone, contacting said solution therein with gas containing H28 and an amount of Q0: i

\ rromnonefto a volume equal to the volume or the 1 7 H 3 content oi said gas while maintaining tem-v perature not less than C. and not more than 125 0., and regulating the contacting operation so as to prevent, during thecourse thereof; in-

crease oi! the total sodiumsalt content?! ot'the solution undergoing H28 gassing, tomore than 21% by weight-expressed as mecca, thereby forming sodium hydrosulphide. 11. ,The method for producing sodium NaaCO: solution containing substantiall no sodium saltothenthan M1200: and having an Nam-concentration not less than 10% and not more'than 21% by weight, introducing said solution into a reaction acne, contacting said solution therein with gas containing notless than 50% ,HsS by volume and an amount 01' CO: ransingiro'm none to a volume equal to halt the volume of. the ms content of said gas, maintaining a during said contacting operationtemperature not less than C. and not'morethan C. and

- regulating the contacting operation so as to' prevent, during the course thereof, increase of the totslsodium salt content" or; the solution undergoing Has gassing. to more that 21% by weight, expressed as H8500. thereby -iorming I v .sodimn hydrosulphide.

cumssmors some;

. h dro-y sulphide which comprises forming an aqueous 

